Detergent and method of preparation



Sept. 20, 1938. F. w. MuNclE 2,130,352 DETERGENT AND lMETHOD oFPREPARATION Filed June 27, 1935 Patented Septe 20, 1938 UITED STATESTENT OFFICE DETEBGENT AND lmTlIQD F PREPARATION Application June 27,

22 Claims.

This invention relates to the art of deterging, Washing, cleaning andthe like and particularly to a newtype of chemical product useful insuch processes and to a process for its manufacture.

rlfhe new products formed and used according to this invention are theresult of the interaction of fatty oils, such as are commonly used insoap making, with glycerine and sulphuric acid. Such products are welladapted to replace soap for domestic use.

Ordinary soaps, that is, the alkali salts of the fatty acids, have beenin useV for many, many years and consequently, the commonly used soapsand the processes of manufacturing them have become quite standardized.To supply the demand, requires large soap manufacturing plants involvinglarge initial investments and large up keep expenditures, this beingmainly due to the fact that the saponication process in large scaleproduction requires kettles of enormous size and ypower sources ofcommensurate size to furnish the necessary heat for the reaction.

The merchandizing of soap, however. has developed into`a highlycompetitive ield, thus reducing the retail selling price of soap andsoap products to a hazardous level from the standpoint of the legitimatemanufacturers with their large plants. The cost price to themanufacturers of good quality basic materials used in soap production isquite uniform and the processes of manufacture are all very much thesame.

Soap, in addition, regardless of the quality of the fats and oilsemployed therein, is well known to have certain objectionablecharacteristics, and :'r, some manufacturers have attempted to meet thekeen price competitionby eliminating some of these characteristics fromthe -products which they produce, thus to win for them by merit a pricewhich will give a reasonable profit. Re- Vsearch to this end has beenintensified during recent years and a large number of new productssuggested for use. 1

' One of the main objections to ordinarysoaps is that they forminsoluble curds with some of 3 the metals that are commonly present inhard water or the materials to be washed. They also have otherdisadvantages, such as being alkaline and having insufficient detergentpower when 'used in hard water. The compounds which have been suggestedto replace soap, and which have to a certain extent already replaced it,are, most of them, sulphonates or sulphates of organic compounds.reveals that they differ widely in their wetting and detergent power,and also in their stability,

An examination of the compounds 1935, Serial No. 28,712

foam producing ability, solubility and in the solubility of their salts;They diler also, of course, in the dimculty of their manufacture, thecost of the raw products necessary to make them, and lin theirstructural formulas.

Among the better known of these compounds that have been suggested toreplace soaps, are the sulphonated alcohols and certain othersulphonated products derived from fatty acids in which the carboxylicacid group has been either neutralized with an amine or esterifled withethyl or a similar alcohol. Each of these types of products has beenfound to have rather desirable characteristics. Most of lthe compoundssuggested are relatively stable to acids and alkalis, have a higherdetergent power in hard water than soap and good emulslfying properties,and form no precipitates with calcium and other metals that are commonlyencountered. However, the diillculty of their manufacture is such thatthey are necessarily quite expensive in comparison with ordinary soaps,and hence, while they have been found commercially feasible for someindustrial uses, particularly in the treatment lof textile materialspreparatory to dyeing, where their stability and the solubility of theirsalts are of particular importance, they do not find a ready market incompetition with ordinary soap for domestic use.

1 Accordingly, it is the purpose of this invention to provide at a costcomparable to the cost of ordinary soap. a material that is superior tosoap in wetting, emulsifying and deterging characteristics especially inhard water, that is nonalkaline, and the metal salts of which arepractically all soluble. To accomplish this object the present inventionprovides a` product that looks, and foams in water much as does ordinarysoap of high quality. The new product, however, has a far greaterdetergent power than soap in hard Water and-leaves no soap curd on thewalls of the vessel in which it is used. Furthermore, this new productmay be formed directly from the fatty oils and some other relativelyinexpensive chemicals without the necessity of first convertf ing thefatty oils to fatty acids and there are no large quantities ofby-products to be removed. Thus the cost of production is sufiicientlylow to enable the new product to compete directly on a price basis withordinary soaps even under the present conditions of keen competition.

In the practice of this i'nventiom fatty oils, which may or may notcontain free fatty acid are reacted with anhydrous or at leastsubstantially anhydrous glycerine and fuming sulphuric 2 ,l acid.Preferably, the'resulting product is thereafter lneutralized. The mannerin' which the compoundsare reacted may be varied. although a procedurewhich has been found particularly satisfactory will be hereinafterdescribed in' detail. Other examples of satisfactory procedures foraccomplishing this reaction are given in a. copending application,Serial No. 28,711, filed June 27, 1935.

Preferably, about two molecular weights of substantially anhydrousglycerine are reacted with one molecular weight of fatty oil and threemolecular weights of fuming sulphuric acid. In order tobring thereaction to completion it has been found desirable to have aconsiderable excess of sulphuric acid present. From this excess aquantity of an inorganic sulphate is formed by the neutralization of theresulting product.

After neutralization, water is usually removed to solidify the product.This may be done by the use of drying rolls or by spraying, in much thesame way that soap is dried. The inorganic sulphate .from theneutralization may either be left as a part of the final' product orremoved, according to the properties desired in the product. Thedeterging effectiveness of the product is'not impaired by the presenceof the inorganic salt, and the mixture has been found satisfactory formost purposes, even when the salt is present, while the elimination ofthe removal step results in a considerable saving. Of course, if theinorganic salt is removed, the concentration of the organic detergentmaterial in the product is increased and hence the deterging power of agiven quantity of the final product is raised accordingly.

In describing, by way of example, an illustrative process by which thenew products may be produced, reference will be had to the accompanyingdrawing in which the process is shown diagrammatically by a `flow sheet.The method illustrated and hereafter described is, however, only givenby way of example, and other methods may be used for the preparation ofthe new products within the scope of this invention.

One method, then, by which a new product has been formed in accordancewith this invention, andas diagrammatically shown in the drawing,consisted in reacting a quantity of fatty oil and glycerine and thenacting on the resulting product with sulphuric acid and finallyneutralizing. For example, to 216 pounds of cocoanut oil there wereadded 64 pounds of anhydrous glycerine (99.5%) and 1.2 pounds of causticsoda. The mixture was heated to 175 to 205 C. for approximately an hourat the end of which time the resulting product was found to be misciblewith 95% ethyl alcohol. The caustic soda apparently acts to catalyze thereaction but ltsuse may be eliminated provided the temperature of thefatty oil and glycerine mixture is raised to ZBO-290 C. and held thereuntil the product is homogeneous and soluble in 95% ethyl alcohol.y

vTo 281 pounds of the product of this firstr reaction there `were nextadded 526 pounds of fuming sulphuric acid (102.8%, which containsapproximately 12x/2% free S03) and the mixture stirred at a temperatureof around 40C. until the resultant product was miscible withwater.Sulphuric acid of this proportion andstrength was found suilicient'to'bring the reaction Ato such a state that a solution of 1% of the product'in water is substantially clear and non-turbid by reacting wlth theglycerine-fatty oil compound and absorbing the water of,reaction. It wasfound aisasea that, in general, enough sulphuric acid should be Iprovided to fulfill the molecular weight requirements given above,namely, three molecular weights for every two molecular weights ofglycerine and one molecular weight of fatty oil, and

in addition there should bc an excess of sulphuricacid suicient toabsorb one molecular weight of water for each molecular weight ofsulphuric acid-- that is to enter the reaction. Since this water needsto be absorbed readily, it is preferable that the amount andconcentration of the excess of sulphuric acid be such that afterabsorbing the The dry material contained around 60% of sodium sulphateand 40% of the organic material -and formed a dry, granular,non-hygroscopicpowder at room temperature.

When warmed somewhat or compounded with an appropriate amount of water,glycerine or mineral oil, it could be milled, plodded or pressed intocakes by the use of the usual soap molding machinery.

The sodium sulphate or other sulphate formed by the neutralization canbe removed, if desired, but this is not usually necessary, and, in fact,the presence of this inorganic salt in the final products, in manyinstances, appears to improve the desirability of the material,particularly for domestic use. The product made according to the firstof the above examples will contain about 60% sodium sulphate. For somepurposes, however, it may be desired to produce a detergent according tothe present invention but free from the inorganic sulphates formed bythe neutralization. To eliminate this inorganic sulphate it has beenfound easier to modify the original process by.

which the material is produced than to attemptA to remove theinorganicsulphate, once it has been formed in the composition.

As an example of a process by which the new materials may be formed andfreed of inorganic salts, the fatty oil, glycerine and sulphuric acidmay be reacted as in the first example above. Then, instead ofneutralizing with caustic soda, about 400 pounds of hydrated lime may beadded to the mixture as a 10% slurry. Calcium sulphate will be formedfrom the excess sulphuric acid and lime and will precipitate. Thecalcium salt of the new detergent product being soluble,

-the mixture may be filtered to remove the calcium sulphate. Preferably,an amount of water equal to the amount of the solution is used to washthe calcium sulphate free of detergent product. The solution, containingthe calcium vsalt of the new material may then be treated with asolution of a suitable calcium precipitant, as, for example,

sodium carbonate or sodium phosphate or sodium oxalate in an amountslightly in excess of that required to replace all of the calcium in thedetergent with sodium and precipitate the calcium as the carbonate,phosphate or oxalate. This precipitate may then be filtered off and theremaining solution is ready for concentration as desired In order tostabilize the new product, the solution may, if .it is found necessary,be ad- 1 aisance rolls. The dried product when warm is soft andflexible, but becomes quite hard and brittle at room temperature. It canbe prepared as .a powder. A 20% aqueous solution of the salt freeproduct is liquid above C.

In some instances, it may be desirable to use the calcium salt of thenew material directly without converting it into the sodium salt and inother cases it may be to advantage to form the corresponding ammonium,triethanoiamine, magnesium, potassium or other salts. These may beformed in the same manner as the sodium salts, or ammonia ortriethanolamine may be added together with carbon dioxide to precipitatethe calcium, instead of adding their carbonates or oxalates.

The calcium salt itself may be dried over a heated roll. In this case, alow temperature-of drying is preferable, since the product has atendency to char. VThe use of vacuum with the roll is desirable. or theproduct may be mixed to a slurry with a filler. such as calciumsulphate, chalk, bentonite, pumice or clay and dried by means of aheated roll.

The saft free product may, however, be formed from the product madeaccording to the example, if so desired, by extracting the product withalcohol to remove the product and leave the inorganic salt.``iiilternatively,Y the product may be extracted before neutralizatiombutafter suiiicient dilution to prevent reaction, with butyl alco hol. Thebutyl alcohol solution is thereafter neutralized with caustic or thelike to the proper pH of around 6.0 to 7.0. Other solvents can be usedin place of the alcohol and butyl alcohol mentioned,

yIn order to aid in the identication of the new products and todemonstrate their effec tiveness as detergents certain tests have beenmade upon a product made according to the first example and containing60% sodium sulphate, .and upon the same product without the sodiumsulphate. The sodium sulphate containing product gave 450 cubiccentimeters of foam when 50 `cubic centimeters of an equeous l solutioncontaining 1% of the material (total Hard water ing material (60% sodiumsulphate) as solution #1 and a. 1% solution of the sodium sulphate freematerial as solution #2 and adding thereto equal volumes of a n ofreagents in 10% solutions and at room temperatin'e, the followingresults V were noted:

No precipitate.

Do. Slight turbidity. N c pecipitate.

precipitateo. No turbidity.

No turbidity cold or hot.

No No ""`A test was also made of the detergent power of several Wellmourn detergents and of the sodium sulphate containing product madeaccording to the rst example above. The standard soil test was used andthe following results obtained with a Pulfrich photometer:

'While cocoanut oil has been named in the above examples, it is to beunderstood that the use of other fatty oils will also result insatisfactory products, varying proportions being used to compensate forthe difference in molecular weights. Among the oils which have beensatisiactorily used are taliow, soy bean oil, and palm oil. In fact.ithas been found, that oils ordinarily considered to be inferior for thepurpose of making soap. may be used according to this invention toproduce products of a very good grade and the use of even such materialsas fish oils and garbage grease is within the scope of this invention.Also, glycol or other polyhydric alcohols may be substituted forglycerine and other sulphating or even phosphating compositions such aspyrophosphoric acid or phosphoric acid containing phosphoric anhydridemay be substituted for sulphur-ic acid. Monoglycerides may also beformed by the reaction with glycerine of fatty Aacids, naphthenicacids', abletic acid or the caruct has been described in the examples asthough i it were a batch process, it is contemplated that by suitablearrangement of equipment the reacting compounds can be caused to yflowcontinuously through a system of apparatus, thus permitting rawmaterials to be reacted in a continuous process to produce the newproducts.

It is not desired in the present application to be in any way bound bythe structural formula which the products herein described are believedto have, or by the chemical reactions which are thought to take placeduring the formation of the products. The oils from which the productsare made are known to be of' a complex nature and the literature andresearches upon the subject fail to give any absolute assurance as tothe reactions that take place or the structural formulas of thecompounds formed. Furthermore, since the oils are complicated mixturesof or. ganic compounds it is possible that the different compounds reactdifferently with the glycerine and sulphuric acid .and it may be thatthis fact accounts for much of the value of the final product.

The following tentative explanation of the reactions and formulas aretherefore given merely in order to aid in understanding this inventionand with the;1;eservatioriv that they are but V.

Laurie acid Myristic acid 20% Capi-ic acid 10% Caprylic acid 9%CHsECHDlO COOH CH3 CH2M: COOH CH3(CH7)8 COOH CH3(CH2)6 COO H Oleic acidCH3(CH:)1 CH:CH(CH2)1 COOH Palmitic acid 5% CHa(CHz)u COOH Stearic acid3% CHa(CH2)1 COOH Caproic acid 2% C-H3(CH2)4 COOH For every threemolecules of fattyacid present -there is, of course, approximately onemolecule of glycerine and when these fatty acids and the glycerine arecombined, three molecules of water are dropped from the composition. Thefatty acids in the oil mjay vary and, of course, will differ when thekind of oil is changed, but by using R as the fatty acid radical, theformula xfor the triglyceride may be considered to be cmooox GnoccaCmooon When one molecule of triglyceride of this formula is reacted withtwo molecules of glycerine it appears that the following reaction maytake This reaction takes place upon the application of heat and is aidedby the presence of caustic soda or other alkali,` soaps, alcoholates,certain metals and other catalysts.

Y ucts may be designated, monoglycerides.

The addition of fuming sulphuric acid to the monoglyceride effects theformatlonof a new product, apparently according to the followingreaction:

CHrOOCR CHlOOCR HOU -l H2504 HOH H10 CHQOH CHiOSOaH This product whenneutralized with caustic soda results in the final product apparently ofthe formula:

CHoocR omoocn CHoH NaOH non 13,0,

CHzOSOaH CHzOSOsNa At the same time any excess of sulphuric acid isconverted into sodium sulphate.

vmouth washes.

The resultant prod- According to the reactions and the formula given,the final product is the monoglyceride sulphate of sodium either with orwithout a quantity of sodium ization.

It is intended thatl the present products shall be used directly inplace of the ordinary soaps, particularly for laundry, toilet uses andgeneral domestic purposes, but it is possible to use the new products incombination either with the ordinary type of soap or with other types ofsulphonated detergents or wetting agents. The new material may becompounded with sodium silicate, talc, pumice; Whiting, feldspar,naphtha, phenols, titanium dioxide, barium sulphate or other materialscommonly incorporated in soap.

The final products may be obtained by `suitable manipulation `in theform of cakes, powder, akes or solutions and are adaptable for use asingredients in shaving, facial or dental creams, liquid shampoos, mouthwashes or.cleansing solutions, shampoo or dental powders, as an additionto dyestu baths and for general detergent purposes either alone or inadmixture with soap. Since the products are not precipitated by mercuryor silver they may also be used to advantage in compounding antisepticorgermicidaldetergents with mercury or silver salts. Furthermore, theproduct has a very much milder taste and odor thanordinary soapsprepared from the same oils and is therefore of particular value indentrices or Also, the material is not precipi-f tated by sea water' orhard water and hence is paricularly valuable where such waters mustr beuse For practical use as a detergent it is important that the materialproduce a clear solution with water. The substantially pure materialproduced according to this invention does this as is show in the datagiven above. i

What I claim is:

1. In a process of forming a composition of matter includingvasubstantial proportion of a salt of a sulphuric acid'ester of amonoglyceride, the steps that comprise reacting a monoglyceride withfuming sulphuric acid of such strength and quantity as will reacttherewith and leave an excess of sulphuric acid in the mixture, whichexsulphate formed in the neutralcess will, after the completion ofthereaction,

have a concentration of not less than about 99.3% sulphuric acid, andthereafter neutralizing the mixture.

2. In a process of forming a composition of matter including asubstantial 'proportion of a salt of a sulphuric acid ester ofalcocoanut oil monoglyceride, the steps thatcomprise reacting cocoanutoil monoglyceride with fuming` sulphuric acid of such strength andquantity as, will react therewith land leave an excess of sulphuric acidin the mixture, which excess will, after the completion of the reaction,have a concentration of not less than about 99.3% sulphuric acid, andthereafter neutralizing the mixture.

3. In a process of forming a composition of matter including asubstantial proportion of a salt of a sulphuric acid ester of a fattyacid monoglyceride, the steps that comprise reacting a fatty acidmonoglyceride substantially free of glycerine and free fatty acid withfuming sulphuric acid of such strengthV and quantity as `will reacttherewith and leave an excess of sulphuric acid in the mixture, whichexcesswill, after the completionx of the reaction, have a concentrationof not less than about 99.3% sulphuric acid; and thereafter neutralizingthe mixture.

4. In a process `oi forming a composition of matter including asubstantial proportion of a salt of a sulphuric acid ester of amonoglyceride of an acid of the group consisting of fatty acids,naphthenic acids, abietic acid, and the carboxylic acids produced by theoxidation of paramn hydrocarbons, the steps that comprise reacting amonoglyceride of an acid of the said group with fuming sulphuric acid ofsuch strength and quantity as will react therewith and leave an excessof sulphuric acid in the mixture, which excess will, after thecompletion of the reaction, have a concentration of not less than about99.3% sulphuric acid, and thereafter neutralizing the mixture.

5. In a process of forming a composition of matter consistingprincipally of a substantially pure salt of a sulphuric acid ester of amonoglyceride, the steps that comprise reacting a monoglyceride withfuming sulphuric acid of such strength and quantity as will reacttherewith and leave an excess of sulphuric acid in the mixture, whichexcess will, after the completion of the reaction, have a concentrationof not less than about 99.3% sulphuric acid, thereafter neutralizing themixture, separating the product from the mixture by extracting withalcohol, and drying.

6. In a process ci forming a composition of matter consistingprincipally oi' a substantially pure salt of a sulphuric acid ester of acocoanut oil monoglyceride, the steps that comprise reacting a cocoanutoil monoglyceride with sulphuric acid of such strength and quantity aswill react therewith and leave an excess of sulphuric acid in the mixture, which excess will, after the completion of the reaction, have aconcentration of not less than about 99.3% sulphuric acid, thereafterneutralizing the mixture, separating the product from the mixture byextracting with alcohol, and drying.

7. In a process of forming a composition of matter including asubstantial proportion of a sulphuric acid ester of a monoglyceride, thestep that comprises reacting a monoglyceride with fuming sulphuric acidof such strength and quantity as will react therewith and leave anexcess of sulphuric acid in the mixture, which excess will,

after the completion oi the reaction, have a concentration of not lessthan about 99.3% sulphuric acid.

8. In a process of forming a composition of matter including asubstantial proportion of a sulp huric acid ester of a cocoanut oilmonoglyceride, the step that c omprises reacting a cocoanut oilmonoglyceride with fuming sulphuric acid of such strength and quantityas will react therewith and leave an excess of sulphuric acid in themixture, which excess will, after the completion of the reaction. have aconcentration of not less than about 99.3% sulphuric'acid.

9. In a process of forming a composition of matter including asubstantial proportion of a sulphuric acid ester of a fatty acidmonoglyceride,

the step that comprises reacting a fatty acid monoglyceridesubstantially free of glycerine and free fatty acid with fumingsulphuric acid of such strength and quantity as will react therewith andleave an excess of sulphuric acid in the mixture, which excess Will,after the completion-of the reaction, have a concentration of not lessthan about 99.3% sulphuric acid.

10. In a process of forming a composition of matter including asubstantial proportion of a sulphuric acid ester of a monoglyceride ofan acid of the group consisting of fatty acids, naphthenic acids,abietic acid, and the carboxylic acids produced by the oxidation ofparain hydrocarbons,

the step that comprises reacting a monoglyceride of an acid of the saidgroup with fuming sulphuric acid of such strength and quantity as willreact therewith and leave an excess of sulphuric Aacid in the mixture,which excess will, after the completion -of the reaction, have aconcentration of not' less than about 99.3% sulphuric acid.

11. In a process of forming a composition of matter including asubstantial proportion of a salt of a sulphuric acid ester of apolyhydric alcohol mono-ester of an acid of the group consisting offatty acids, naphthenic acids, abietic acid, and the carboxylic acidsproduced by the oxidation of petroleum hydrocarbons, the steps thatcomprise reacting a polyhydric alcohol mono-ester of an acid of thegroup consisting of fatty acids, naphthenic acids, abietic acid, and thecarboxylic acids produced by the oxidation of petroleum hydrocarbonswith fuming sulphuric acid of such strength and quantity as will reacttherewith and leave an excess of sulphuric acid in the mixture, whichexcess will, after the completion of the reaction, have a concentrationof not less than about 99.3% sulphuric acid, and thereafter neutralizingthe mixture.

12. In a process of forming a composition of matter including asubstantial proportion of a salt of a sulphuric acid ester of apolyhydric alcohol mono-ester of a cocoanut oil fatty acid, the stepsthat comprise reacting a polyhydric alcohol mono-ester of a cocoanut oilfatty acid with fuming sulphuric acid of such strength and quantity aswill react therewith and leave an excess of sulphuric acid in themixture, which excess will, after the completion of the reaction, have aconcentration of not less than about 99.3% sulphuric acid, andthereafter neutralizing the mixture.

13. In a process of forming a composition of matter including asubstantial proportion of a sulphuric acid ester of a polyhydric alcoholmonoester of an acid of the group consisting of fatty acids, naphthenicacids, abietic acid, andthe carboxylic acids produced by the oxidationof petroleum hydrocarbons, the step that comprises reacting a polyhydricalcohol mono-ester of an acid of the group consisting of fatty acids,naphthenic acids, abietic acid, and the carboxylic acids produced by theoxidation of petroleum 'hydrocarbons with fuming sulphuric acid of suchstrength and quantity as will react therewith and leave an excess ofsulphuric acid in the mixture, which excess will, after the completionof the reaction, have a concentration of not less than about 99.3%sulphuric acid.

14. In a process of forming a composition of matter including asubstantial proportion of a 'sulphuric acid ester of a polyhydricalcohol monomatter including a/substantial proportion of a sulphuricacid ester of a polyhydric alcohol mono ester of a cocoanut oil fattyacid, the step that comprises reacting a polyhydric alcohol monoester ofal cocoanut oil fatty acid with -fuming sulphuric acid of such strengthand quantity as will react therewith and leave an excess of sulphuricacid in the mixture, which excess will, after the completion of thereaction, have a concentration of not less than about 99.3% sulphuricacid.

l16. The process of forming a composition of matter including asubstantial proportion of a salt of a sulphuric acid ester of amonoglyceride comprising reacting anhydrous glycerine, fatty oil, andfuming sulphuric acid, the oil and glycerine being present insubstantially the proportions of 1 mol of fatty oil to 2 mols ofglycerine and the sulphuric acid being of such strength and quantity aswill react and leave an excess of sulphuric acid in the mixture, whichexcess will, after the completion oi the reaction, have a concentrationof not less than about 99.3% sulphuric acid and thereafter neutralizingthe mixture.

17. 'I'he process of forming a composition of matter including asubstantial proportion of a sulphuric acid ester" of a monoglyceridecomprising reacting anhydrous glycerlne, fatty oils, and fumingsulphuric acid, the oil and glycerine being present in substantially theproportions of 1 mol. of `fatty oil to 2 mols of glycerine and thesulphuric acidbeing Aof such strength and quantity as will react 'andleave an excess of sulphuric acid inthe mixture, which excess will,after the completion of the reaction, have a concentration of not lessthan about 99.3% sulphuric acid.

18. In a process of forming a composition of matter including asubstantial proportion of a salt of a sulphuric acid ester of amonoglyceride, the steps that comprise reacting a monoglyceride withfuming sulphuric acid of such strength and quantity as' will reacttherewith and leave an excess of sulphuric acid in the mixture, whichexcess will, after the completion of the reaction,

have a concentration of not less than about 99.3% sulphuric acid,thereafter neutralizing the mixture with an agent of the groupconsisting of hydroxides, oxides, and carbonates of the alkaline earthmetals, separating the inorganic sulcess, will, after the completion ofthe reaction, have a concentration of not less than about 99.3%sulphuric acid, thereafter neutralizing the mixture with calciumhydroxide,b separating calcium sulphate from the mixture, reacting themixture with sodium carbonate, and removing the resultant calciumcarbonate.

20. In a process of forming a composition of matter including asubstantial proportion of a salt of a sulphuric acid ester of amonoglyceride, the steps that comprise reacting a monoglyceride withfuming sulphuric acid of such strength and quantity as will reacttherewith and leave an excess of sulphuric acid in the mixture, whichexcess will, after the completion of the reaction, have a concentrationof not less than about 99.3% sulphuric acid, thereafter neutralizing themixture with an agent of the group consisting of hydroxides, oxides, andcarbonates of the alkaline earth metals, separating the inorganicsulphate from the mixture, reacting the mixturewith a salt of an acidcapable of forming water insoluble salts with alkaline earth metals,said salt having a positive ion selected from the group consisting ofalkali metals, ammonium, and organic bases, and removing the resultantalkaline earth metal salt.

2l. In a process of forming a composition of matter including a salt ofa sulphuric acid ester of a monoglyceride and an inorganic salt, thesteps that comprise reacting a monoglyceride with fuming sulphuric acidof such strength and quantity as Will react therewith and leave anexcess of sulphuric acid in the mixture, which excess will, after thecompletion of the reaction, have a concentration of notless than about99.3% sulphuric acid, and thereafter neutralizing the mixture.

22. In a process of forming a composition of matter including a salt ofa sulphuric acid ester of a monoglyceride and a by-product salt, thesteps that comprise reacting a monoglyceride with fuming sulphuric acidof such strength and quantity as will react therewith and leave anexcess of sulphuric acid in the mixture, which excess Will, after thecompletion of the reaction, have a concentration of not less than aboutmixture, and spray drying the mixture.

FRED WEAVER MUNCIE.`

